Novel perfumery uses of {90 -cyanotricyclene

ABSTRACT

Processes and compositions are described for altering the aroma of consumable products including perfumes, perfume compositions and perfumed articles utilizing as the essential ingredient an organic tricyclene derivative having the formula:

United States Patent [191 Mookherjee et al.

[ Dec. 23, 1975 NOVEL PERFUMERY USES OF ar-CYANOTRICYCLENE [75] Inventors: Braja Dulal Mookherjee, Matawan;

Venkatesh Kamath, Red Bank, both of N.J.; Edward J. Shuster, Brooklyn, NY.

[73] Assignee: lntemational Flavors & Fragrances Inc., New York, NY.

22 Filed: Mar. 10,1975

21 Appl. No.: 556,874

52 us. Cl. 252/522; 260/464; 260/468 0;

v 5 260/6755 51 int. cl. A61K 7/46; c113 9/00 58 Field or Search. .7 252/522; 260/675.5, 464

[56] 1 References Cited UNITED STATES PATENTS l/l956 Bluestone et al. 260/586 O OTHER PUBLICATIONS Arctander, Perfume and Flavor Chemicals (1969): Compound Nos. 641, 764, 1064, i439 and 1451.

EXAMPLE I 1T cyqnotricyclene Primary Examiner-Herbert Levine Assistant Examiner-G. E. Schmitkons Altomey, Agent, or Firm-Arthur L. Liberman, Esq.; Harold Haidt, Esq.

[5 7] ABSTRACT Processes and compositions are described for altering the aroma of consumable products including perfumes, perfume compositions and perfumed articles utilizing as the essential ingredient an organic tricy clene derivative having the formula:

4 Claims, 2 Drawing Figures SOLVENT: CDCI3 J IOOOHz SWEEP SIGNAL "AMPLITUDE M lo 9 v a, 7 6

U.S. Patent Dec. 23, 1975 FIG.!

EXAMPLE I TT- cyanofricyclene H w W P E E W S 2 H 0 o D l 0 PPM FREQUENCY (cm-U WAVELENGTH IN MICRONS EXAMPLE I TT- cyunotricyclene FIG.2

NOVEL PERFUMERY USES OF 1T-CYANOTRICYCLENE BACKGROUND OF THE INVENTION There is a continuing search for materials having desirable fragrance properties. Such materials are sought either to replace costly natural materials or to provide new fragrances or perfume types which have not heretofore been available. Especially desirable qualities for substances having interesting fragrances are stability and persistence in a wide variety of perfumed articles and perfume compositions, ease of manufacture, and intensity of aroma.

Woody, orrisey, melony, herbal, patchouli-like, green, fruity and camphoraceous notes are particularly desirable for many uses in conjunction withperfumes and perfumed compositions and articles.

Various nitriles not containing the tricyclene moiety have been described as being useful in altering the organoleptic characteristics of fragrances for use in conjunction with perfume compositions and perfumed articles. v

Arctander, Perfumefand Flavor Chemicals (Aroma Chemicals) 1969 contains the following teachings:

i. At No. 1451, the perfume use ofgeranylnitrile;

ii. At No. [439, the perfume use of geranyl isobutyronitrile;

iii. At No. 641, the perfume use of cinnamyl nitrile;

iv. At No. 764, the perfume use of beta(2,6,6-

trimethyl-2-cyclohexenyl) vinyl cyanide.

v. At No. 1.064, the perfume use of 2,2-dimethyl-3- 2,6,6 trimethyl-.2-cyclohexen-l -yl)-propionitrile having either of the structures:

This material is described as having a sweet and floral, rather pungent odor, with balsamic undertones". No

' such materials have been discovered, wherein the combination of woody, orrisey, melony, herbal, patchoulilike, green, fruity and camphoraceous notes notes exist.

THE INVENTION It has now been discovered that perfume formulations, perfumed materials and perfumed articles having one or more of woody, orrisey, melony, herbal, patchouli-like, green, fruity and camphoraceous notes may be provided by adding rr-cyanotricyclene having the structure:

lll

to perfume and fragrance-modifying materials or to materials to be fragranced (e.g., soaps or detergents).

The preparation of 'rr-cyanotricyclene is carried out by reacting analkali metal cyanide with a ar-halo tricyclene having the generic formula:

wherein Y is a halogen selected from the group consisting of chloro, bromo and iodo, Examples of alkali metal cyanide useful in the reaction are sodium cyanide and potassium cyanide. The reaction is carried out in an inert solvent such asdimethyl sulfoxide at a temperature in the range of from C up to 100C; preferably C. Themole ratio of alkali metal cyanide to rr-halo tricyclene is fromlOzl up to 20:1 with a mole ratio of 15:] being preferred.

It has been found that the rr-cyanotricyclene of this invention possess one'or more woody, orrisey, melony, herbal, patchouli-like, green, fruity and camphoraceous notes with good intensity and persistence. This fragrance quality particularly adapts the 'rr-cyanOtricy clene for incorporation into perfume compositions and fragrance-modifying compositions having desirable Pine Needle Oil aromas. It will be appreciated by those skilled in the art from the present disclosure that the fragrance character of the finished perfume compositions can be tailored to specific uses; as more fully described hereinafter.

The ar-cyanotricy'clene is an. olfactory agent and can be incorporated into a wide variety of compositions which will be enhanced by any of the woody, orrisey, melony, herbal, patchouli-like, green, fruity and camphoraceous notes. The rr-cyanotricyclene can be added to perfume compositions in its pure form or it can be added to mixtures of materials in fragrance-imparting compositions to provide a desired fragrance character to a finished perfume material. The perfume and fragrance compositions obtained according to this invention are suitable in a wide variety of perfumed articles and can also be used to enhance, modify or reinforce natural fragrance materials. It will thus be appreciated that the rr-cyanotricyclene of this invention is useful as an olfactory agent and fragrance.

The term perfume composition is used herein to mean a mixture of compounds, including, for example, natural oils, synthetic oils, alcohols, aldehydes, ketones, esters, lactones, and frequently hydrocarbons 3 which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain (a) the main note or the bouquet or foundationstone of the composition; (b) modifiers which roundoff and accompany the main note; fixatives which NaCN include odorous substances which lend a particular note to the perfume throughout all stages of evaporation; and substances which-retard evaporation; and (d) top-notes which are usually low-boiling fresh-smelling materials. Such perfume compositions of this invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants and the like.

In perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus, the 1r-cyanotricyclene of this invention can be used alone or in combination to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient of the composition.

The amount of rr-cyanotricyclene of this invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as much as 50% or as little as 0.6% by weight of mixtures or compounds of this invention, or even less can be used to impart one or more woody, orrisey, melony, herbal, patchouli-like, green, fruity and camphoraceous aromas to soaps, cosmetics, and other products. The amount employed will depend on considerations of cost, nature of the end product, the effect desired in the finished product, and the particular fragrance sought.

The 'rr-cyanotricyclene disclosed herein can be used alone or in a fragrance-modifying composition, or in a perfume composition as olfactory components in detergents and soaps, space deodorants; perfumes; colognes; bath preparations such as bath oil, bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun screens; powders such as talcs, dusting powders, face powder and the like. When the rr-cyanotricyclene of this invention are used in perfumed articles such as the foregoing, it can be used in amounts of 0.1 percent or lower. Generally, it is preferred not to use more than about percent in the finished perfumed article, since the use of too much will tend to unbalance the total aroma and will needlessly raise the cost of the article.

The following examples serve to illustrate embodiments of the invention as it is now preferred to practice it. It will be understood that these examples are illustrative and the invention is to be considered restricted thereto only as indicated in the appended claims.

4 EXAMPLE 1 Preparation of rr-Cyanotricyclene Reaction:

Into a 500 ml 3-neck, round bottom flask equipped with condenser, thermometer, mechanical stirrer, hot water heating bath and N purge is charged 200 cc distilled dimethyl sulfoxide. 21.6 g (0.1 moles) of rr-bromotricyclene is then added into the 500 ml flask containing the 200 ml of dimethyl sulfoxide. While stirring and purging with nitrogen 77.6 g (1.58 moles) of sodium cyanide is then added. Heating by means of the hot water bath to C is then effected, and the 90C temperature is maintained for 22 hours. The reaction mass is then cooled to 40C (below which temperature it becomes solidified) and 200 ml of water is added thereto. The aqueous phase is then extracted with five ml portions of petroleum ether. The combined petroleum ether extracts are then washed with three 50 ml portions of saturated sodium chloride solution and dried over anhydrous MgSO The dried extract is filtered and the solvents are evaporated yielding 21.2 g of crude product.

The crude product is distilled on a 2 inch rush-over column and collected three fractions. While distilling the condenser has to be heated as the pure nitrile solidifies.

Distillation Data:

NMR, mass spectral and [R analyses confirm that fractions 1 and 2 consist essentially of vr-cyanotricyclene having the structure:

The mass spectral analysis of 1r-cyanotricyclene in order of decreasing intensity is as follows:

The NMR spectrum of rr-cyanotricycfehe is set forth in FIG. 1 and its IR spectrum is set forth in FIG. 2.

EXAMPLE II r P'ine Needle Perfume Formulation The following mixture is prepared: 2

Ingredient Parts by Weight 11 -Cyanotricyclene (prepared 50 according to the process of Example I) Tcrpentine Gum Oil 100, Limenone i 50 Isohornyl Acetate I00 Orange Oil 25 Gum Camphor Lauryl Aldehyde P" 3 Borneol 50 Terpineol Palatone 3-hydroxy-2-methyl- 4-pyrone) The rr-cyanotricyclene imparts a greensmelony, herbaceous character so necessary for pine-needle oil.

EXAMPLE III Preparation of Soap Composition One hundred grams of soap chips are mixed with one gram of the perfume composition of Example II until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent Pine Needle character with a green, melony, herbaceous character.

EXAMPLE IV Preparation of a Detergent Composition A total of I00 grams of a detergent powder is mixed with 0.l5 grams of the perfume composition of Example II until a substantially homogeneous composition is obtained. This composition has an excellent Pine Needle oil odor with a green, melony, herbaceous character.

EXAMPLE V Preparation of a Cosmetic Powder Composition A cosmetic powder is prepared by mixing in a ball mill I00 grams of talcum powder with 0.25 grams of 'rr-cyanotricyclene produced according to Example I. It has an excellent woody, camphoraceous, orrisey aroma.

EXAMPLE VI Perfumed Liquid Detergent Concentrated liquid detergents with a woody, camphoraceous and orrisey odor are prepared containing 0.10 percent, 0.15 percent and 0.20 percent of 1rcyanotricyclene. They are prepared by adding and homogeneously mixing the appropriate quantity of 'rr-cyanotricyclene in the liquid detergent. The detergents all possess a woody, camphoraceous, orrisey fragrance, the intensity increasing with greater concentration of rr-cyanotricyclene.

EXAMPLE VII Preparation of a Cologne and Handkerchief Perfume 1r-Cyanotricyclene is incorporated in a cologne at a concentration of 2.5 percent in 85 percent aqueous ethanohand into a handkerchief perfume at a concentrationof 20 percent (in percent aqueous ethanol). A distinct and definite strong woody, camphoraceous, orrisey fragrance is imparted to the cologne and to the handkerchief perfume.

EXAMPLE VIII The composition of Example II is incorporated in a cologne at a concentration of 2.5 percent in 85 percent aqueous ethanol; and into a handkerchief perfume at a concentration of 20 percent aqueous ethanol). The use of the 1r-cyanotricyclene in the composition of Example II affords a distinct and definite strong Pine Needle type perfumearoma having a green, melony and herbaceous character to the handkerchief perfume and cologne.

EXAMPLE IX Preparation of Soap Composition" One hundred grams of soap chips are mixed with one gram of the rr-cyanotricyclene of Example I until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent woody-patchouli character with camphoraceous, orrisey and fruity notes. I

EXAMPLE X I Preparation of a Detergent Composition A total of I00 grams of a detergent powder is mixed with 0.15 grams of the qr-cyanotricyclene of Example I until a substantially homogeneous composition is obtained. This composition has an excellent woody, patchouli odor with camphoraceous, orrisey and fruity notes.

EXAMPLE XI Preparation of a Cosmetic Powder Composition A cosmetic powder is prepared by mixing in a ball mill, grams of talcum powder with 0.25 grams of the composition of Example II. It has an excellent Pine Needle Oil character.

EXAMPLE XII Perfumed Liquid Detergent lll and at least one adjuvant selected from the group consisting of natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, esters and lactones.

2. A perfumed article comprising vr-cyanotricyclene having the structure: N

lll

4. A cologne composition comprising 'rr-cyanotricy- C :N clene having the structure:

lll

and a detergent, soap, bath preparation, hair preparatron, cosmetic preparation or powder.

3. A process for preparing a perfumed composition comprising the step of admixing a composition of matter with a fragrance-imparting amount of 1r-cyanotricyand ethanol and water. clene having the structure: 

1. A PERFUME COMPOSITION COMPRISING $-CYANOTRICYCLENE HAVING THE STURCUTRE:
 2. A perfumed article comprising pi -cyanotricyclene having the structure:
 3. A process for preparing a perfumed composition comprising the step of admixing a composition of matter with a fragrance-imparting amount of pi -cyanOtricyclene having the structure:
 4. A cologne composition comprising pi -cyanotricyclene having the structure: 